Nov. 20, 1953
NOTES
5747
k t t e r may be readily converted to the former. phenyl)cyclohexane-l,2-diol, m.p. 104-105", identical the product described by Bergmann, et aZ.* !Conformationalanalysis of the trans-glycol requires with 2-( 2,J-Dimethoxypheny1)-cyclohexane-1 ,2-diol Acetonide. the arrangement: 2-phenyl (e), 2-hydroxyl (p), -The glycol (2 g.) was dissolved in acetone (200 ml., dis1-hydroxyl (p) while in the cis-glycol the following tilled from anhydrous potassium carbonate) and was shaken arrangement obtains : 2-phenyl (e), 2-hydroxyl mechanically with anhydrous copper sulfate (10 g.) for 96 After filtration and evaporation of the solvent under (p), 1-hydroxyl (e). It is implied in the work hours. reduced pressure, the residue was dissolved in chloroform of Beckett, Pitzer and Spitzer3 that the energy and chromatographed over alumina. The acetonide (2.1 difference in similar systems between 2(p), (e) and 9.) passed through the column readily and any glycol still (p), 2(e) is of the order of 1 kcal./mole. It has, present remained in the column. The analytical sample of the oily acetonide was prepared by heating the material indeed, been shown that the molar heat of com- in a high vacuum a t 70' for 24 hours. bustion in the case of the cis-glycol is 1563.1 kcal. Anal. Calcd. for C17H2404: C, 69.83; H , 8.27. Found: and that of the trans-glycol, 1564 k ~ a l . ~ C, 70.10; H, 8.16. A novel method has recently been employed by In the infrared spectrum, the hydroxyl band present in the Woodward for the synthesis of cis-glycols5 based glycol a t 2.86 p , was completely absent. A strong band a t upon Winstein's work on neighboring group effects6 9.68 p and a band of medium intensity a t 11.35 p were The method involves the trans addition of iodine present .* to a double bond followed by attack by silver ace(8) For the position of the ether bands in the infrared specfra of tate to give the trans-iodoacetoxy compound. acetonides, see R. B. Woodward, el c l . , THISJOURNAL, 74, 4241 The presence of water in the acetic acid used as (1952). solvent leads to the formation of the cis-glycol CONVERSE MEMORIAL LABORATORY UNIVERSITY monoacetate. Finally, saponification leads to the HARVARD CAMBRIDGE 38, MASS. cis-glycol. When applied to 1-(2,3-dimethoxyphenyl)-cyclohexene, this method led to the same glycol obtained by the standard hydroxylation procedures. That Reaction of Some Metallic Oxides with Liquid the stable conformation in this case is, indeed, the Dinitrogen Tetroxide. Oxides of the First and Second Periodic Groups and Lead' cis-glycol was shown by the preparation of an acetonide using anhydrous copper sulfate as catalyst. BY JOHN R. FERRARO AND GEORGE GIBSON Acetonide formation proceeds a t a slow rate beRECEIVED JUNE 25, 1953 cause one of the hydroxyl groups is tertiary, but is This is the first of a planned series of studies being practically complete within 96 hours. Although cases of trans-glycols forming acetonides are known undertaken at this Laboratory on the reaction of when mineral acid is used as catalyst' due to prior liquid dinitrogen tetroxide with various oxides. rearrangement to the cis-glycol, no such cases have Other workers have studied reactions of the oxides ~ ~ * Hg04 and ZnOj5 been reported when copper sulfate is used as Ca0,2 CuO and C U ~ O , Pb0,4 with gaseous or liquid Nz03or Nz04. The oxides catalyst. Experimental studied in this series are listed in Table I. cis-2-( 2,3-Dimethoxyphenyl)-cyclohexane-l,2-diol.-1(2,3-Dimethoxyphenyl)-cyclohexene(4.77 9.) was dissolved in analytical glacial acetic acid (100 ml.) in a three-necked flask equipped with stirrer, reflux condenser and thermometer. Silver acetate (8.22 9.) was added followed by finely powdered iodine (5.85 9.) in small portions to the vigorously stirred reaction mixture over a period of 30 minutes at room temperature. During this time the temperature rose from 26 t o 33'. When all the iodine had been absorbed, as indicated by the color of the mixture, aqueous acetic acid (9.85 ml. prepared by dilution of 2.0 ml. of water up t o 50 ml. with glacial acetic acid) was added and the reaction mixture was heated in a boiling water-bath with vigorous stirring for 3 hours. After cooling, sodium chloride (20 g.) was added, the mixture was stirred for 30 minutes more and the insoluble precipitate was removed by filtration. The precipitate was washed with hot benzene and the combined filtrate was evaporated under reduced pressure. The residue was treated with methanol, filtered to remove a small amount of insoluble material, and to the filtrate was added a solution of potassium hydroxide (2 9.) in methanol (10 ml.). After hydrolysis had proceeded overnight, the methanol was removed under reduced pressure, water was added and the mixture was extracted with ether. Removal of the solvent and trituration of the residue with methylcyclohexane yielded 3 . 2 g. (56%) of cis-2-(2,3-dimethoxy(3) C. W. Beckett, K . S. Pitzer and R . Spitzer, THISJOURNAL, 69, 2488 (1947). (4) P . E.Verkade, et al., A n n . , 467,217 (1928). ( 5 ) We are indebted t o Dr. R . B. Woodward for making this information available to us and for kindly assenting to its disclosure prior to his own publication of the details of the method. (6) Cf. S. Winstein and R . E. Buckles, THISJOURNAL, 64, 2787 (1942). (7) Cf. A. A. Petrov, J . Gen. Chrm. ( U . S . S . R . ) , 10, 981 (1940); C. A . , S6, 3603 (1941).
Experimental Materials.-PbsOd, PbOe, BaOz, BaO (71% Ba(OH)a), CuzO, HgO, HgzO and Hg(NO8)p were reagent grade chemicals. PbO, ZnO, PbO and MgO were prepared by the thermal decomposition of the respective carbonates and CaO and SrO from their oxalates. AgzO and CuO were prepared by precipitation from solution with NaOH, followed by drying to the oxide. NzOd (cylinder) was dried before use by passing through a PzOa drying tower. Analyses.-Dinitrogen tetroxide content (as NOz) in the reaction products was determined by cerate oxidation, as previously described.8 Copper and mercury determinations were done by standard electrolytic procedures. Calcium, cadmium, lead, zinc and magnesium were determined gravimetrically by ignition of the reaction product t o the oxide. Water analyses were done by the standard Karl Fischer procedure. Apparatus and Procedure.-The apparatus and experimental procedure have been described elsewhere.6 The reactants were heated to 87' a t 14.5 atm. NO2 pressure except for Ca(OH)2, HgO, HgZO and Hg(NO8)n which reacted completely a t 25' and 1.1 atm. NO2 pressure. All transfers or operations on the products were carried out in a dry-box. (1) Presented in part at the 122nd Meeting of the American Chemical Society, September, 1952. (2) M . Ostwald, Ann. chim., (IX) 1,32 (1914);J . R.Partington and F. A. Williams, J . C h e w Soc., 186, 947 (1924); E.Briner, J. P . Lugrin and R . Monnier, Relu. China. Acta, 19, 64 (1930). (3) E. Divers and T . Shimidzu, J . Chem. SOL., Trans., 4T, 630 (1885); J. R. Park and J. R . Partington, J . Chrm. Soc., lS6, 72 (1924); J. R.Partington, { b i d . , 1111, 663 (1924). (4) G.Boh, Ann. chim., SO, 421 (1945). (5) C.C.Addison, J. Lewis and R. Thompson, J . Chem. Soc., 2829, 2838 (1951); C.C.Addison and J. Lewis,ibid., 2833 (1961). (6) G.Gibson and J. J, Kate, THXB JOURNAL, 78,5436 (1951).
5748
NOTES
Vol. 75
8 7 O , however, the solid product increased in bulk volume some tenfold over that of the original oxide, producing a jade green micro-crystalline solid. Metal(I1) Reaction Oxide NO2 in cation In all of these experiments a considerable excess of time, reacted, product, in product, Oxide hr 70 "0 % dinitrogen tetroxide liquid was present after rePbO 7 84 Xila action] but in the case of the copper(1) reaction] 86* Xi1 PbaOi 9 only about 0.5 ml. of the 20 to 30 mole excess was PbOn 7 97 Nl observed as free liquid. Apparently the reaction I1 100 2.06 AgzO product has the ability to absorb a large quantity ZnO 6 5 100 37 84c 19.14' of the excess dinitrogen tetroxide present; howCdO 7 80 1 61 ever, no reduction in the bulk volume of the solid fi 3 90 26.84' 11 96' product was observed when the excess liquid diMgO CaO 6 50 0 81 nitrogen tetroxide was pumped off. It is interest100 Nil ing to note that the reaction product of copper(I1) Ca(OH),d 350 days' SrO 14 5 0 0 22 oxide did not exhibit this property. BaOs 8 25 .13 blercury(1) and (11) oxides and anhydrous Bad 14 5 99 .24 mercury(I1) nitrate reacted with the liquid diCUO 14.5 85 31.94' 22 95' nitrogen tetroxide to produce brown viscous oils cu,o 7 5 100 32.03 22 43 which were immiscible in the solvent. The oily 400 days' 100 19.53 47 95 product could be frozen with liquid nitrogen to a HgO 100 16 87 HgzO 16 days' yellow glass-like solid having a conchoidal fracture. Nil = 0.1% or less by weight of NO2. Residual oxide The softening point of this material was slightly Pb304 by X-ray diffraction pattern. Corrected for unre- below the freezing point of liquid dinitrogen tetroxacted oxide in product. Ca(NO()z.HsO isolated: Found: ide. Hg(NO&.2NO2 remained as an oil a t 25 to HtO, 9.52. ThFory: HzO, 9.88. e Time (in days), indicates the time the oxide remained in contact with N204 prior t o 30' in a nitrogen dioxide gas atmosphere of 750 analysis rather than the time for actual reaction. Observ- mm., but lost NO2 very rapidly below this pressure able reaction occurred in these cases in from 4 to 48 hours. at 30°, yielding a pale yellow solid having a com71% Ba(0H)Z. position approximating Hg(NO3)~0,7N02. This latter product when heated gave mercury(I1) Results and Discussion The data in Table I are representative of several nitrate. The reaction of anhydrous mercury(I1) experiments for each of the listed oxides, prepared nitrate with liquid dinitrogen tetroxide was carried at low temperatures. Confirming previous ob- out far the purpose of confirming the composition servation~,~.~ the oxides prepared at higher tem- of the oily product obtained for the oxides. Hg(N0&.2N02 is the most unstable of these nitrogen peratures were much less reactive. dioxlde-containing compounds investigated to date. The catalytic effect of water on oxide-liquid Hg(N03)2,2N02 may be the same compound reNz04 reactions is illustrated by the data for Caported by Boh4 as his unidentified product obtained (OH), and BaO (71% Ba(OH)2). The products were either the corresponding from the reaction of mercury(I1) oxide and dinitroanhydrous nitrates or the NO2 addition compounds gen trioxide. Acknowledgments.-The authors wish to thank of the following analytical composition: Mg(N03)2.N021211(N0~)~.2.6 to 3.3 NO2, Cu(N03)~. Messrs. M. Brodsky and I. Kalnin of the Chemis2N02 and Hg(N03)2.2N02. These addition com- try Department for their assistance in preparing pounds were decomposed to the anhydrous nitrates the X-ray patterns mentioned above; also the at mm. and at temperatures ranging from 90 Argonne National Laboratory for the loan of the to 140', depending upon the thermal stability bomb tube apparatus used in this research. of the particular compound. The preparation of DEPARTMENT OF CHE~USTRY Mg(NOJ2 was not particularly successful due, we ILLINOIS INSTITUTE OF TECHNOLOGY 16, ILLINOIS believe, to a concurrent decomposition of the CHICAGO Mg(N03)2. Zinc oxide heated in the presence of liquid Divergent Electrophoretic Properties of Dissolved dinitrogen tetroxide gave as a product a light and Adsorbed Trypsin brown, viscous oil, which solidified completely to a BY ROBERTA S . HARTMAN, J. B. BATEMANAND H. E. light yellow, waxy solid in approximately eight EDELHOCH hours. The same solid product was obtained with RECEIVED JULY 20, 1953 zinc oxide and liquid dinitrogen tetroxide at room temperature. We believe Z I I ( N O ~ ) ~ .to ~ . ~3.3 There is good experimental evidence that the NO2 represents a mixture of Zn(N03)2.2N204 electrophoretic mobilities of inert particles susZ ~ I ( N O ~isolated )~ at 30' whereas Addison6 ob- pended in a protein solution (microscope method) tained Zn(N03)2.2N204a t 15'. In this series of are often not greatly different from the mobility of addition compounds, Zn(N03)2.2N204is inter- the dissolved protein, as determined by the moving mediate in thermal stability between Cu(NO& boundary method under comparable conditions of 2N02 and Hg(NO&2N02. PH, ionic strength, etc.' However, large differThe copper(1) oxide exhibited a rather unusual ences have been noted with several proteolytic behavior toward liquid dinitrogen tetroxide. At L. S. Moycr, J . Biol. Chcm., 122, 641 (1938); H.A. Abramson, room temperature there was no observable reaction L. (1) S Mover and M. H. Gorin, "Electrophoresis of Proteins," Reinbold other than a slight darkening of the oxide. A t Puli1 C'ttrp , h-ew York. N.Y.,1942. TABLE I REACTION OF OXIDSSWITH LIQUIDNz04
f
+
